Reaction rate | EPFL Graph Search

The reaction rate or rate of reaction is the speed at which a chemical reaction takes place, defined as proportional to the increase in the concentration of a product per unit time and to the decrease in the concentration of a reactant per unit time. Reaction rates can vary dramatically. For example, the oxidative rusting of iron under Earth's atmosphere is a slow reaction that can take many years, but the combustion of cellulose in a fire is a reaction that takes place in fractions of a second. For most reactions, the rate decreases as the reaction proceeds. A reaction's rate can be determined by measuring the changes in concentration over time. Chemical kinetics is the part of physical chemistry that concerns how rates of chemical reactions are measured and predicted, and how reaction-rate data can be used to deduce probable reaction mechanisms. The concepts of chemical kinetics are applied in many disciplines, such as chemical engineering, enzymology and environmental engineeri

Fast temperature cycling of the catalytic CO oxidation using microstructure reactors

Martin Luther

The possibility to increase the performance (productivity or selectivity) of a chemical reactor by using periodic variations of reaction parameters (e.g. reactant concentration or temperature) has been theoretically envisaged since the beginning of the 70th. The experimental validation of the predicted positive effects was successful in the case of concentration variation but failed for temperature variation. This was mainly due to the high thermal inertia of the conventional chemical reactors used for the measurements which prevented to create variations having a sufficiently high frequency. Microstructure reactors own, at the contrary to conventional reactors, a very low thermal inertia and allow to generate temperature oscillations with an amplitude of about ten to hundred Kelvin at a frequency in the order of magnitude of 10-1 to 4 Hz. These properties, coupled with the possibility to introduce a catalytic active material within the devices, seem to make them well suited for the study of the effects of fast periodic temperature variations of a catalytic reaction. The objective of this work was to demonstrate that non-stationary temperature conditions may increase the reaction rate of a heterogeneously catalyzed reaction up to values not predicted by the classical Arrhenius dependency towards the temperature. Two different types of microstructure reactors have been used. The reaction was taking place in the first one (FTC-type 2) in microstructured channels on whose walls a catalytic layer was deposed. In the second one (FTC-type 3), the reaction was taking place on a piece of sintered metal fibres (SMF) plate placed in a reaction chamber. The catalytic active material was deposed on the SMF plate filaments. Both devices where permanently heated by electrical resistors and periodically cooled down with water flowing through cooling channels incorporated in the devices. The test reaction chosen for the experimental measurements was the CO oxidation reaction, heterogeneously catalyzed by platinum supported on alumina (Pt/Al2O3). The reaction behaviour under stationary thermal conditions was consistent with the one predicted by the Arrhenius law. The dependency of the reaction rate with the temperature was exponential with an apparent activation energy of 104 kJ·mol-1, a negative partial reaction order for CO and a positive one for O2. The measurements effectuated under quasi-stationary thermal conditions (slow temperature ramps) have shown that a temperature change rate between 7 and 14 K·min-1 was not sufficient to observe any non-trivial effect of the temperature. The reaction behaviour was always predicted by the Arrhenius law. The surface coverage of the reactive species is, in this case, always able to follow the slow temperature changes and the reaction behaves as being always under steady-state conditions. The experiments realized under non-stationary thermal conditions using the FTC-type 2 reactor have also failed to demonstrate any non-trivial effects of the temperature oscillations. This device allows indeed to generate temperature oscillations with an amplitude of up to 120 K with a frequency of 0.1 Hz but unfortunately correlated with a very high thermal inhomogeneity. A temperature difference of up to 80 K was measured between a cold spot and a hot spot inside the device. Due to their very low local reaction rate the colder areas of the reactor have attenuated the product concentration (CO2) oscillations which should have been created by the temperature variations. This attenuation prevented the temperature oscillations to have any positive effect compared to the stationary thermal conditions. The FTC-type 3 reactor allowed temperature changes of lower amplitude but the thermal homogeneity was much better. The maximal temperature difference measured between two points within the reactor was only 15 K. Under temperature oscillation conditions, the measured instantaneous CO2 concentration was higher for any temperature within the oscillation range compared to the one recorded under stationary thermal conditions. The increase obtained in the mean CO2 concentration was ranging from 34% for a frequency of the oscillations of 0.035 Hz to 85% for a frequency of 0.052 Hz. The amplitude of the oscillations was kept constant at approximately 40 K and the mean temperature value at 437 K. The simulations effectuated using a theoretical model for the catalytic CO oxidation including a feed-back step in the form of the oxidation-reduction of the catalyst have shown that the experimentally observed increase may be qualitatively explained. Above a certain frequency, the temperature oscillations are fast enough compared to the characteristic time of the feedback step and are able to perturb the stationary established reactive species surface coverage. The formation of a transient surface coverage more favourable for the reaction than the surface coverage at high temperature allows during the transient period to reach an instantaneous surface reaction rate values higher than the one at high temperature. This reaction rate peak is then responsible for the increase of the mean reaction rate under non-stationary thermal conditions and, thus, for an increased yield.

EPFL2008

Incremental Identification of Kinetic Models by Online Spectroscopy and Multivariate Calibration

Laurent Brandinu

Extent-based kinetic identification is a modeling technique that uses number of moles / concentrations measurements to compute extents and identify reaction kinetics (partial orders of reactions and reaction rate constant) by the integral method of parameter estimation. This project uses infrared spectroscopic data with calibration models to predict moles / concentrations via a PLS1 regression method. The calibration set (design of experiment) is constructed from a seven-level design for multivariate calibration in molar fraction with reacting material. The extent-based kinetic identification using number of moles predicted from spectroscopic data is tested through experiments in a homogeneous liquid-phase reaction system. The experiments were conducted in an RC1 calorimeter from Mettler Toledo with two inlet streams, without outlet stream, and a ReactIR 10 FT-IR probe. The reaction studied was the transesterification of methanol and hexanol with acetic anhydride producing methyl, hexyl acetate and acetic acid. No solvents or catalyst were used, only pure species at a reaction temperature of 50°C. Results in terms of calibration design and model, computation of extents and extent-based kinetic identification are discussed.

2015

Integrating Rate Based Models into a Multi-Objective Process Design & Optimisation Framework using Surrogate Models

Levent Sinan Teske

In the development of energy and chemical processes, the process engineers extensively apply computer aided methods to design & optimise these processes and corresponding process units. Such applications are multi-scale modelling and multi-objective optimisation methods. Multi-objective optimisation of super-structured process designs are expensive in CPU-time due to the high number of potential configurations and operation conditions to be calculated. Thus single process units are generally represented by simple models like equilibrium based (chemical or phase equilibrium) or specific short cut models. In the development of new processes, kinetic effects or mass transport limitations in certain process units may play an important role, especially in multiphase chemical reactors. Therefore, it is desirable to represent such process units by experimentally derived rate based models (i.e. reaction rates and mass transport rates) in the process flowsheet simulators used for the extensive multi-objective optimisation. This increases the trust engineers have in the results and allows enriching the process simulations with newest experimental findings. As most rate based models are iteratively solved, a direct incorporation would cause higher CPU-time that penalises the use of multi-objective optimisation. A global surrogate model (SUMO) of a rate based model was successfully generated to allow its incorporation into a process design & optimisation tool which makes use of an evolutionary multi-objective optimisation. The methodology was applied to a fluidised bed methanation reactor in the process chain from wood to Synthetic Natural Gas (SNG). Two types of surrogate model, an ordinary Kriging interpolation and an artificial neural network, were generated and compared to its underlying rate based model and the chemical equilibrium model. The analysis showed that kinetic limitations have significant influence on the result already for standard bulk gas chemical components. A case study applying the previous version of the process design model and the revised version (with rate based model introduced as a set of five surrogate models) will demonstrate that the prediction uncertainties of the process design & optimisation methodology are reduced due to the integration of the rate based model of the fluidised bed methanation reactor. It will be shown that the different process design models predict considerably different optimal operating conditions of the Wood-to-SNG process. This emphasises the importance of the integration of rate based models into the process design models. The presented approach has been developed for the fluidised bed methanation reactor, however, it is a generic approach which can be applied to other process unit technologies as well. Future investigations will target other technologies to further improve the process design & optimisation predictions and support project development.

EPFL2014